Photoconductive material for electrophotography

ABSTRACT

WHEREIN X is CN or COOR&#39;&#39;, R is hydrogen atom, halogen atom, OR&#39;&#39; or COOR&#39;&#39;, and R&#39;&#39; is alkyl group having one to four carbon atoms.   A photoconductive material comprising an electroconductive support having coated thereon a layer containing a sensitizer, a plasticizer and a high-molecular compound having the following repeating unit:

United States Patent i [is] 3,647,428

Ono et al. Mar. 7, 1972 [54] PHOTOCONDUCTIVE MATERIAL FOR 3,058,959 10/1962 Bailey et al. ..260/86.l N ELECTROPHOTOGRAPHY 3,554,741 1/1971 Gipstein et a1 ..96/1,5 X [72] Inventors: l-lisatake Ono; Syu Watarai; Harumi Katprimary g g F Lesmes y i of Asakai J 1 Assistant Examiner-R. E. Martin [73] Assignee: Fuji Photo Film (30., Ltd., Kanagawa, AmmeyAddams and Ferguson Japan [57] ABSTRACT [22] Filed: Nov. 27, 1970 A photoconductive material comprising an electroconductive PP 93,337 support having coated thereon a layer containing a sensitizer, a plasticizer and a high-molecular compound having the fol 301 Foreign Application Priority om Peatmg 1- Nov. 28, 1969 Japan..- ..44/95990 I' I cH/rc I [52] US. Cl. ..96/1.5,.260/85.5 R, 260/85.5 B, L X J 0H1 260/86.1 N, 260/47 UA, 117/201, 117/211, CH,

117/161 UN, 252/501, 96/1.6 [51] Int. Cl. G033 5/06 [58] FieldofSearch ..96/l.5; 260/85.5 R, 85.5 B,

260/86.1 N, 47 UA wherein X is CN or. COOR', R is hydrogen atom, halogen [56] dam Cited atom, OR or COOR' and R is an alkyl group having 1 one to four carbon atoms.

UNITEDSTATES PATENTS w 1. a r V,

2,798,061 7/1957 Cooveretal ..260/85.5B 3,028,372 4/1962 Kocay et a1. .260/85.5R 1 r i s PHOTOCONDUCTIVE MATERIAL FOR ELECTROPHOTOGRAPHY This invention relates to a photoconductive material for electrophotography. As photoconductive substances useful There are metallic plates, papers having an electrophotoconductively and plastic films as electroconductive bases providing preferable results.

Useful plasticizers which are used for the purpose of imfor l ph p y there have heretofofe l known 5 proving film properties include chlorinated paraffins, Such morgamc compfmnds as Selemum and Zmc oxlde, Such chlorinated bipheny], phosphate type plasticizers and phthalow ("game Qompounds as anthracene, chl'ysene late type plasticizers. The amount in which they are added is in f benzldme and Such mqlecular compounds as the range of 0 to 100 percent by weight based on the aforevinylcarbazole, polyvinylriaphthalene and mentioned high molecular compounds polyvmylfmthracene' As sensitizers for increasing the sensitivity, there can be An object 9 the pre sent mvemlon to pmv'de m used such known compounds as tetracyanoethylene, tetraphotoconductwe T i ctrophotography havmg cyanoquinodimethane, chloranil, bromanil, naphthoquinone, novel structure, which IS entirely different from such heretoanthraquinone, methylene blue, crystal violet, and malachite fore known compounds.

. green. Desirable results are obtained when such sensitizers are The organic photoconductive materials for electrophotogi5 added in the amount not exceeding 10 percent by weight on raphy according to this invention are high molecular compounds having the following repeating units the total film composmon' H i. It is desirable that the combination of these ingredients, is F C l 1 coated on the electroconductive base in such a thickness that L I T the film on drying has a thickness of 2-20 The photosensi- X RN CH3 tive layer consequently obtained is uniformly charged through H3 corona discharge by the usual method, then exposed to light projected through an image, and developed by cascade R developing process or liquid developing process to produce a t-.. w developed image. (Whercm x represents CN COOR', R represents hydrogen Now the present invention is described in more detail by atom, a halogen atom, CR or COOR', and R represents a referring to preferred embodiments lower alkyl group such as methyl, ethyl, propyl, or butyl In case where any of the aforementioned compounds is used EXAMPLE I as a photoconductive material for electrophotography, it is dissolved in a suitable solvent such as tetrahydrofuran, 100 Parts of tetrahydwfurani there were dlssolvFd acetone, toluene or benzene and then is casted or coated on Parts of 132 copolymer 7 15 0-175 and molficular welght an electroconductive base so as to form a photosensitive layer. 41,700). of i' hy and In this case, by adding a plasticizer and a sensitizer to the soluacrylonlmlei Parts of chlwmated dlphenyl and 1 P of tion, the properties f the photosensitive layer can be bromanil. The resultant solution was coated on an aluminum proved and, at the same time, the sensitivity thereof can be Pri to a y ttilllckness of abilmt iPi" y g of 3" greatly enhanced. t e ayer was c arged positive y in ar p ace and, with a l in High molecular compounds for the present invention can be containing a positive image placed thereon, exposed for 1 obtained by mixing l-alkyl-2-methylene-3,S-dimethylindoline second to light from a l00-watt tungsten bulb positioned upderivatives with electron-acceptive olefines such as 40 wardly at a distance of 30 cm., and then treated with a acrylonitrile and acrylesters at desired ratios, adding to the developing agent containing therein a negatively charged resultant mixtures such radical polymerization initiators as t n r. Consequently,the positive image was developed. When azo'bis'isobutyl'onitrile thendheating the reactants in a the layer was placed in the atmosphere to trichloroethylene, current of nitrogen in a egasse System there resulted fixin to roduce a clear ima e.

To cite a concrete example of synthesis, 42 g. of 1,3,3- 45 g P g trimethyl-2-methylenindoline, 26 g. of acrylonitrile and 0.1 g. EXAMPLE [I of azo-bis-isobutyronitrile are placed in a lOO-ml. three-neck y the Same procedure as in Example I a photosensitive flask and, while under supply of nitrogen gas and simultaneous l o ayer was obtained from 1.2 copolymer (['1 is 0.10 and agitation, allowed to react for 3 hours at 85 C. The viscosity mo] I Wei ht is 7 600) of 1 3 Ltrimeth e of reaction solution is increased and becomes glutinous. When at l Th b y h y this is poured into 2 liters of methanol being vigorously dome and et yacry mug F f agitated. the polymer settles down while the unreacted sure, developing and fixing, there was obtained aclear image. monomer is dissolved in the methanol. Through subsequent EXAMPLE m filtration and drying, there is obtained 21 g. of polymer. The intrinsic viscosity of polymer is 0.175 in tetrahydrofuran at 30 By the same procedure as in Example I, a sensitiveflaygr C. prepared from 1:5 copolymer ([1 is 0.12) o l,

In the similar manner, various copolymers can be obtained tetramethyl-Z-methyleneindoline and acrylonitrile. Through by the combinations of monomers as shown in the following subsequent charging, exposure, developing, and fixing, there table. H 0 CH3 was obtained a clear image.

Mono A; a Similar results to those to the examples were obtained by using, in the same procedure, 1:2 copolymer of l-ethyl-2- E I =CH2 methylene-3,3-dimethylindoline and acrylonitrile, 1:5 copolymer of l,3,3-trimethyl-2-methylene-S-chloroindoline and ethylacrylate, 1:5 copolymer of l,3,3-trimethyl-2- l methylene-5-carboethoxyindoline and acrylonitrile, 1:5 MONOMER B B1 t" 1 f copolymer of l,3,3-trimethyl-2-methylene-5-methoxyindoline ectron-accep we 0 e in Monomer A Substit- Substit- Number uent R uent R Boiling point Monomer B i%3 c$i?nfat:: iiggfi gocn. CH; 129 C./6 mm. Hg OHFCHCOOCHZ CH; 132: C./6 mm. Hg 8%: i $315213: origonooobim and acrylonitrile, 1:2 copolymer of 1,3,3-trimethyl-2- methyleneindoline and methyl-acrylate, and l:5 copolymer of l,3,3-trimethyl-Z-methyleneindoline and n-butylacrylate What is claimed is: g l. A photoconductive material comprising an electroconductive support having coated thereon a layer containing a high molecular compound having the following repeating unit:

ong-011 052- 1 L R-N/ om CH3 (wherein X is CN or COOR', R is hydrogen atom, halogen atom, OR or COOR', and R is an alkyl group.)

2. A photoconductive material comprising an electroconductive support having coated thereon a layer containing a plasticizer and a high molecular compound having the following repeating unit:

CH CH ea -ca wherein X is CN or COOR', R is hydrogen atom, halogen atom, OR or COOR', and R is an alkyl group having one to four carbon atoms. 

2. A photoconductive material comprising an electroconductive support having coated thereon a layer containing a plasticizer and a high molecular compound having the following repeating unit:
 3. A photoconductive material comprising an electroconductive support having coated thereon a layer containing a sensitizer, a plasticizer and a high molecular compound having the following repeating unit: 